Search Results (46)

The electrocaloric effect (ECE) has become one of the most intensively studied topics in ferroelectrics, with dozens of new papers that report experimental results and provide increasingly extensive data compilations every year. However, the heterogeneity of the literature, arising from differences in compositions, dopants, preparation routes, measurement protocols, and analysis methods, makes direct comparison between studies highly problematic. In this work, we focus on barium titanate (BaTiO₃) as a representative lead-free ferroelectric system. BaTiO₃ was chosen because, within this class of materials, it offers by far the largest body of reported ECE results, obtained under a wide range of experimental conditions, thus allowing for the most comprehensive characterization. Using this example, we explore whether meaningful patterns related to the influence of chemical substitution on the magnitude and temperature dependence of the ECE can be discerned. In addition, we critically examine why certain comparisons reported in the literature may be misleading or inherently unreliable. Finally, we discuss predictive approaches, including those employing artificial intelligence algorithms, and evaluate their applicability and limitations in modeling the electrocaloric response. Full article

BaTiO₃ (BT)-based lead-free ceramics are regarded as highly promising candidates for solid-state electrocaloric (EC) cooling devices due to their large spontaneous polarizations, shiftable Curie temperatures, and environmental friendliness. This review summarizes recent progresses in the design and optimization of BT-based EC ceramics. Key aspects include thermodynamic principles of the EC effect (ECE); structural phase transitions; and strategies such as constructing relaxor ferroelectrics, multi-phase coexistence, etc. Finally, future research directions are proposed, including the exploration of local microstructural evolution, polarization flip mechanisms, and bridging material design and device integration. This work aims to provide insights into the development of high-performance BT-based materials for solid-state cooling devices. Full article

Electrocaloric materials, which exhibit adiabatic temperature change under an applied electric field, are promising for solid-state cooling technologies. In this study, the electrocaloric response of lead-free Ba_xCa_1−xZr_yTi_1−yO₃ (BCZT) ceramics was modeled to investigate the effects of composition, processing, and measurement conditions on performance. A high-accuracy XGBoost regression model (R² = 0.99, MAE = 0.02 °C) was developed using a dataset of 2188 literature-derived data points to predict and design the electrocaloric response of BCZT ceramics. The feature space incorporated compositional ratios, processing parameters, measurement settings, and atomic-level Magpie descriptors, along with Curie temperature to account for phase-transition behavior. Feature importance analysis revealed that electric field, measurement temperature, and proximity to the Curie point are the most critical factors influencing ΔT_EC. Bayesian optimization was applied to navigate the design space and identify performance maxima under unconstrained and realistic constraints, offering valuable insights into the nonlinear interactions governing electrocaloric performance. Under room temperature and moderate-field conditions (24 °C, 40 kV/cm), the optimized ΔT_EC achieved a value of 1.03 °C for Ba_0.85Ca_0.15Zr_0.40Ti_0.60, to be processed at 1090 °C for 3 h during calcination, 1300 °C for 2 h during sintering. By integrating experimental insight with machine learning and optimization, this study offers a refined, interpretable framework for accelerating the design of high-performance electrocaloric ceramics while reducing the experimental workload. Full article

In this study, we characterize electrocaloric lead scandium tantalate (PST) samples by means of the adiabatic temperature change $\Delta T_{\mathrm{ad}}$ and the dissipative heat $q_{\mathrm{diss}}$ with a direct thermal method. The figure of merit ($FOM$), defined as the ratio between the adiabatic temperature change and the thermal hysteresis, quantifies the losses of the material. Additionally, it is also possible to draw conclusions on the efficiency of a caloric cooling system based on the regenerator or cascaded approach. The maximum adiabatic temperature change of the measured samples results in $\Delta T_{\mathrm{ad},\max }=(1.39\pm 0.02)$ K and the dissipative heat yields $q_{\mathrm{diss}}=(0.39\pm 0.05) \mathrm{J}/(\mathrm{k}\mathrm{g} \mathrm{K})$, resulting in an $FOM=(5.1\pm 0.2)$. The efficiency for an ideal cascaded system is given by ${\eta }_{\mathrm{cas}}=0.56$, and for the ideal regenerator, the efficiency is given by ${\eta }_{\mathrm{reg}}=0.84$. The results demonstrate that the PST material in this study exceeds the maximum $FOM$ in the literature by 34%. Full article

In order to obtain large room-temperature electrocaloric effect (ECE) and wide operation temperature range simultaneously in lead-free ceramics, we proposed designing a relaxor ferroelectric with a T_m (the temperature at which the maximum dielectric permittivity is achieved) near-room temperature and glass addition. Based on this strategy, we designed and fabricated lead-free 0.76NaNbO₃–0.24BaTiO₃ (NN-24BT) ceramics with 1wt.% BaO–B₂O₃–SiO₂ glass addition, which showed distinct relaxor ferroelectric characteristics with strongly diffused phase transition and a T_m near-room temperature. Based on a direct measurement method, a large ΔT (adiabatic temperature change) of 1.3 K was obtained at room temperature under a high field of 11.0 kV mm⁻¹. Additionally, large ECE can be maintained (>0.6 K@6.1 kV mm⁻¹) over a broad temperature range from 23 °C to 69 °C. Moreover, the ECE displayed excellent cyclic stability with a variation in ΔT below ±7% within 100 test cycles. The comprehensive ECE performance is significantly better than other lead-free ceramics. Our work provides a general and effective approach to designing lead-free, high-performance ECE ceramics, and the approach possesses the potential to be utilized to improve the ECE performance of other lead-free ferroelectric ceramic systems. Full article

In this work, the electrocaloric effect (ECE) and electrocaloric strength (ΔT/E) were measured and thermal and dielectric studies were performed on Pb-modified BaTiO₃ (BPT). The saturated hysteresis loops and normal ferroelectric behavior of the ferroelectric ceramics allow the utilization of the indirect method to estimate the electrocaloric properties. The electrocaloric measurements were performed under high (18 kV/cm) versus low (8 kV/cm) electric field conditions. These conditions were chosen to notice and then eliminate an artificial negative electrocaloric effect in the tested ceramics. At the same time, relatively high values of positive electrocaloric temperature change ΔT ($~ 2.19 \mathrm{K}$) and electrocaloric strength ΔT/E ($~$0.27–0.11 K$·$cm/kV) were obtained. Full article

BaTiO₃-Bi(Zn,Ti)O₃ (BT-BZT) ceramics have been used as capacitors due to their large dielectric permittivity and excellent temperature stability and are good candidates for lead-free materials for electrocaloric and energy storage devices. However, BT-BZT ceramics often suffer from inferior properties and poor reproducibility due to heterogeneous compositional distribution after calcination and sintering. In this work, (1−x)BT-xBZT ceramics (x = 0~0.2) were fabricated with nano-sized BaTiO₃ raw materials (nano-BT) by a solid-state reaction method to enhance the chemical homogeneity. The (1−x)BT-xBZT ceramics prepared from the nano-BT showed larger densities and more uniform microstructures at the lower calcination and sintering temperatures than the samples prepared from more frequently used micrometer-sized raw materials BaCO₃, TiO₂, Bi₂O₃, and ZnO. The (1−x)BT-xBZT ceramic prepared from the nano-BT displayed a phase transition from a tetragonal ferroelectric to a pseudo-cubic relaxor in a narrower composition range than the sample prepared from micro-sized raw materials. Larger adiabatic temperature changes due to the electro-caloric effect (ΔT_ECE) and recoverable energy storage density (U_rec) were observed in the samples prepared from the nano-BT due to the higher breakdown electric fields, the larger densities, and uniform microstructures. The 0.95BT-0.05BZT sample showed the largest ΔTECE of 1.59 K at 80 °C under an electric field of 16 kV/mm. The 0.82BT-0.18BZT sample displayed a U_rec of 1.45 J/cm², which is much larger than the previously reported value of 0.81 J/cm² in BT-BZT ceramics. The nano-BT starting material produced homogeneous BT-BZT ceramics with enhanced ECE and energy storage properties and is expected to manufacture other homogeneous solid solutions of BaTiO₃ and Bi-based perovskite with high performance. Full article

Pulse-magnetron-sputtered long-term superhydrophilic coatings have been synthesized to functionalize the surfaces of solid-state cooling devices, e.g., electrocaloric heat pumps, where not only a complete wetting of the surface by a fluid is intended, but also fast wetting and dewetting processes are required. The coatings consist of a (Ti,Si)O₂ outer layer that provides lasting hydrophilicity thanks to the mesoporous structure, followed by an intermediate WO₃ film that enables the reactivation of the wettability through visible light irradiation, and a W underlayer which can work as a top electrode of the electrocaloric components thanks to its suitable electrical and thermal conductivity properties. Process parameter optimization for each layer of the stack as well as the influence of the microstructure and composition on the wetting properties are presented. Finally, water contact angle measurements, surface energy evaluations, and a contact line dynamics assessment of evaporating drops on the coatings demonstrate that their enhanced wetting performance is attributed not only to their intrinsic hydrophilic nature but also to their porous microstructure, which promotes wicking and spreading at the nanometric scale. Full article

The versatile electrocaloric (EC) behaviors of the (1-x)Pb(Mg_1/3Nb_2/3)O₃-xPT (PMN-100xPT) single crystal are closely related to the multiple phase transitions under the multiple fields of electric field and temperature. In this work, the EC effect of <001>-oriented PMN-30PT single crystals with chemical composition at morphotropic phase boundary has been studied during the phase transformation process from the ferroelectric rhombohedral (R) phase to the tetragonal (T) phase. Two consecutive negative EC peaks have been achieved for the first time. Based on the projection of the EC effect in the electric field-temperature phase diagram, the relationship between the EC behaviors and the phase transitions is further established. It was found that the monoclinic (M) phase actually existed during the transformation from the R phase to the T phase, and the related R-M phase transition and M-T phase transition could both induce negative EC peaks. Under the electric field of E = 10 kV/cm, the first negative EC peaks induced by the R-M phase transition is at 57 °C with ΔT_max = −0.11 K. And the M-T phase transition can produce a higher negative EC peak, and its value can reach −0.22 K at 68 °C. Based on thermodynamic calculations, the relationship between the entropy change in different phase transitions and the EC behaviors has been further elucidated. The negative EC effect originates from the structural entropy increase in the electric field-induced phase transition process. This work not only advances the research on the electrical properties of relaxor ferroelectric single crystals but also provides a new insight into high-performance ferroelectric materials design. Full article

The paper reports on effect of grain-growth inhibitors MgO, Y₂O₃ and MnCO₃ as well as Ca modification on the microstructure, dielectric, ferroelectric and electrocaloric (EC) properties of Ba_0.82Sr_0.18Sn_0.065Ti_0.935O₃ (BSSnT). Furthermore, the effects of the sintering time and temperature on the microstructure and the electrical properties of the most promising material system Ba_0.62Ca_0.20Sr_0.18Sn_0.065Ti_0.935O₃ (BCSSnT-20) are investigated. Additions of MgO (x_MgO = 1%), Y₂O₃ (x_Y2O3 = 0.25%) and MnCO₃ (x_MnCO3 = 1%) significantly decreased the mean grain size of BSSnT to 0.4 µm, 0.8 µm and 0.4 µm, respectively. Ba_0.62Ca_0.20Sr_0.18Sn_0.065Ti_0.935O₃ (BCSSnT-20) gained a homogeneous fine-grained microstructure with an average grain size of 1.5 µm, leading to a maximum electrocaloric temperature change |ΔT_EC| of 0.49 K at 40 °C with a broad peak of |ΔT_EC| > 0.33 K in the temperature range from 10 °C to 75 °C under an electric field change of 5 V µm⁻¹. By increasing the sintering temperature of BCSSnT-20 from 1350 °C to 1425 °C, the grain size increased from 1.5 µm to 7.3 µm and the maximum electrocaloric temperature change |ΔT_EC| increased from 0.15 K at 35 °C to 0.37 K at 20 °C under an electric field change of 2 V µm⁻¹. Our results show that under all investigated material systems, BCSSnT-20 is the most promising candidate for future application in multilayer ceramic (MLC) components for EC cooling devices. Full article

The new xMnAs/(1 − x)PMN–PT (x = 0.2, 0.3) multicaloric composites, consisting of the modified PMN–PT-based relaxor-type ferroelectric ceramics and ferromagnetic compound of MnAs were fabricated, and their structure, magnetic, dielectric properties, and caloric effects were studied. Both components of the multicaloric composite have phase transition temperatures around 315 K, and large electrocaloric (~0.27 K at 20 kV/cm) and magnetocaloric (~13 K at 5 T) effects around this temperature were observed. As expected, composite samples exhibit a decrease in magnetocaloric effect (<1.4 K at 4 T) in comparison with an initial MnAs magnetic component (6.7 K at 4 T), but some interesting phenomena associated with magnetoelectric interaction between ferromagnetic and ferroelectric components were observed. Thus, a composite with x = 0.2 exhibits a double maximum in isothermal magnetic entropy changes, while a composite with x = 0.3 demonstrates behavior more similar to MnAs. Based on the results of experiments, the model of the multicaloric effect in an MnAs/PMN–PT composite was developed and different scenario observations of multicaloric response were modeled. In the framework of the proposed model, it was shown that boosting of caloric effect could be achieved by (1) compilation of ferromagnetic and ferroelectric components with large caloric effects in selected mass ratio and phase transition temperature; and (2) choosing of magnetic and electric field coapplying protocol. The 0.3MnAs/0.7PMN–PT composite was concluded to be the optimal multicaloric composite and a phase shift ∆φ = −π/4 between applied manetic fields can provide a synergetic caloric effect at a working point of 316 K. Full article

Environmentally friendly lead-free K_1-xNa_xNbO₃ (KNN) ceramics possess electromechanical properties comparable to lead-based ferroelectric materials but cannot meet the needs of device miniaturization, and the corresponding thin films lack theoretical and experimental studies. To this end, we developed the nonlinear phenomenological theory for ferroelectric materials to study the effects of non-equiaxed misfit strain on the phase structure, electromechanical properties, and electrical response of K_0.5Na_0.5NbO₃ epitaxial films. We constructed in-plane misfit strain ($u_1-u_2$) phase diagrams. The results show that K_0.5Na_0.5NbO₃ epitaxial film under non-equiaxed in-plane strain can exhibit abundant phase structures, including orthorhombic $a_{1}c$, $a_{2}c$, and $a_1{a}_2$ phases, tetragonal $a_1$, $a_2$, and $c$ phases, and monoclinic $r_{12}$ phases. Moreover, in the vicinity of $a_{2}c-r_{12}$, $a_{1}c-c$, and $a_1{a}_2-a_2$ phase boundaries, K_0.5Na_0.5NbO₃ epitaxial films exhibit excellent dielectric constant ${\epsilon }_{11}$, while at $a_{2}c-r_{12}$ and $a_{1}c-c$ phase boundaries, a significant piezoelectric coefficient $d_{15}$ is observed. It was also found that high permittivity ${\epsilon }_{33}$ and piezoelectric coefficients $d_{33}$ exist near the $a_{2}c-a_2$, $a_1{a}_2-r_{12}$, and $a_{1}c-a_1$ phase boundaries due to the existence of polymorphic phase boundary (PPB) in the KNN system, which makes it easy to polarize near the phase boundaries, and the polarizability changes suddenly, leading to electromechanical enhancement. In addition, the results show that the K_0.5Na_0.5NbO₃ thin films possess a large electrocaloric response at the phase boundary at the $a_1{a}_2-r_{12}$ and $a_{1}c-a_1$ phase boundaries. The maximum adiabatic temperature change $\mathsf{\Delta }T$ is about 3.62 K when the electric field change is 30 MV/m at room temperature, which is significantly enhanced compared with equiaxed strain. This study provides theoretical guidance for obtaining K_1−xNa_xNbO₃ epitaxial thin films with excellent properties. Full article

Caloric cooling systems are potentially more efficient than systems based on vapour compression. Electrocaloric cooling systems use a phase transformation from the paraelectric to the ferroelectric state by applying or removing an electric field to pump heat. Lead scandium tantalate (PST) materials show a first-order phase transition and are one of the most promising candidates for electrocaloric cooling. To model caloric cooling systems, accurate and thermodynamically consistent material models are required. In this study, we use a phenomenological model based on an analytical equation for the specific heat capacity to describe the material behaviour of bulk PST material. This model is fitted to the experimental data, showing a very good agreement. Based on this model, essential material properties such as the adiabatic temperature change and isothermal entropy change of this material can be calculated. Full article

The annealing effects on Pb_0.97La_0.03Sc_0.45Ta_0.45Ti_0.1O₃ (PLSTT) ceramics prepared by the solid-state reaction method are systemically investigated using experimental and theoretical techniques. Comprehensive studies are performed on the PLSTT samples by varying annealing time (AT) from t (=0, 10, 20, 30, 40, 50 and 60) h. The properties involving ferroelectric polarization (FP), electrocaloric (EC) effect, energy harvesting performance (EHP) and energy storage performance (ESP) are reported, compared and contrasted. All these features are seen to gradually improve with the increase in AT, and they all reach the climaxed-shaped values and then decrease by further increasing the AT. For t = 40 h, the maximum FP (23.2 µC/cm²) is attained at an electric field of 50 kV/cm, while the high EHP effects (0.297 J/cm³) and positive EC are achieved (for ΔT~0.92 K and ΔS~0.92 J/(K·kg)) at 45 kV/cm. The EHP value of the PLSTT ceramics increased by 21.7% while the polarization value was enhanced by 33.3%. At t = 30 h, the ceramics have attained the best ESP value of 0.468 J/cm³ with an energy loss of 0.05 J/cm³. We strongly believe that the AT plays a crucial role in the optimization of different traits of the PLSTT ceramics. Full article

This paper reports on the influence of sintering additives CuO and MgO on the recently developed lead-free electrocaloric (EC) material Ba_0.82Sr_0.18Sn_0.065Ti_0.935O₃ (BSSnT-18-6.5). Details on the sintering behavior and the resulting microstructure of bulk ceramic samples prepared through solid-state synthesis and their dielectric, ferroelectric, and electrocaloric properties are presented. On the one hand, the addition of CuO (x_CuO = 2%) significantly reduced the sintering temperature from 1400 °C to 1150 °C. On the other hand, the addition of MgO (x_MgO = 1%) dramatically reduced the average grain size from 40 µm to 0.4 µm, leading to an increase in dielectric breakdown strength from 4.4 V µm⁻¹ to 7.7 V µm⁻¹. Thus, BSSnT-18-6.5 with the addition of MgO to bulk ceramic samples could achieve maximum EC temperature changes (|ΔT_EC|) of 0.27 K around 30 °C with almost no aberration within a broad temperature range from 5 °C to 50 °C under an applied electric field change of 5 V µm⁻¹. The results show the potential of this material for the fabrication of multilayer ceramic (MLC) components for future electrocaloric applications. Full article